Coal spray composition



United Stat Patent 0 p Oil Company, Chicago, Ill., a corporation of Indiana No Drawing. Application December 18, 1956 Serial No. 628,990

9 Claims. (Cl. 106-278) The present invention relates to coal spray oils and the like and to the treating of solid carbonaceous lump fuels to prevent the formation of dust and other degradation products. 1

Various oils and other materials have been applied in the past to solid carbonaceous lump fuels, particularly coal, lignite, etc., for the purpose of allaying dust, and more particularly for the purpose of preventing degradation known as slacking. This degradation is caused partly by the escape of moisture from the coal and partly by the oxidation of mineral material, particularly iron sulfide, contained in the cleavage veins of coal and similar fuels. Another important problem is that of dusting caused by mechanical abrasion. All of these phenomena are highly undesirable from the standpoint of the ultimate user and result as well in the loss. of valuable fuel.

As disclosed in U.S. 2,383,543 issued to W. Gray, Au-- gust 28, 1945, the use of solven extracts and compositions containing solvent extracts as coal spray oil con stituents have been found to be advantageous for the prevention of degradation. Such extracts may be obtained from petroleum oils by the use of selective solvents such as Chlorex (beta beta dichlorethyl ether), phenol, cresol, furfural, nitrobenzene, chloraniline, chlorphenol,

sulfur dioxide, mixtures of two or more of these solvents,

or other solvent mixtures such as benzol-acetone, benzolmethyl ethyl ketone, phenol containing a small amount of water, etc. The extracts contain aromatic and/or poly-nuclear naphthenic compounds, while the ratfinate contains mono-nuclear naphthenic stocks and/or relatively parafiinic materials.

Such solvent extracts as used as such or are subjectedto an oxidation treatment as described in U.S. 2,319,942 issued to C. C. Miller May 25, 1943. As described in said patent, the oxidation of the solvent extract can be carried out in any desired manner, but particularly good results are obtained by air blowing the extract at a temperature of from about 300 F. to about 550 F. for at least one-half hour; or until there is a substantial increase in the viscosity of the extract.

It is an object of the present invention to provide new and improved coal spray compositions which will prevent the degradation of the coal. Another object of my invention is to provide coal spray materials which will prevent degradation and at the same time give a fuel which is free from undesirable staining characteristics. A further object of my invention is to provide coal spray compositions which will accomplish a given degree of dust-proofing with a smaller amount of material than has heretofore been necessary. A still further object of my invention is to provide coal spray materials which will form uniform films on lump fuels, even when not initially applied to the entire surface of such fuels. It is also an object of my invention to provide coal spray methods having the advantages enumerated. Other and more detailed objects, advantages and uses of my invention will become apparent as the description thereof proceeds.

Iodine value -1 80-95 Acid value 180-192 Saponification value 185-19 5 Unsaponifiable 2.0% max. Color, Gardner 1 12 max. Neutralization equivalent 290-310 Refractive index at 25 C 1.4919. Specific gravity at 15.5. C./15.5 C. 0.95 Flash point, F. 530 Fire point, F. 600- Viscosity at 25 C. (Gardner-Holdt) Z4 Viscosity at 25 C., centistokes 10,000 100 Viscosity at 100 C., centistokes I 2,913,349 Patented ov. 17, 1959 2 lit has been found that a very much improved coal spray composition comprises from about 0.25% to about 5% of a polymeric carboxylic acid, from about 20% to about 50% of a diluent hydrocarbon oil, from about 40% to about of a solvent extract as above defined, and from about 0% to about 30%, preferably from formulation is a polymeric high molecular weight unsat urat'ed carboxylic acid having a molecular weight above about 300, and preferably containing from about 30 to about 60 'carbon atoms in the molecule and at least two carboxyl groups. While substantially pure polymeric fatty acids, such as dimerizedlinoleic acid, can be used, it is preferred, because of their availability, to use commercial polymerized high molecular weight unsaturated carboxylic acids, having a molecular weight above about 300. Y

A useful, commercially available dimeric carboxylic acid is commercially available from Emery Industries, Inc., under the trade name Emery 955-Dimer Acid. Since the commercial product is produced by dimerization of linoleic acid, it is usually referred to as dilinoleic acid. The commercial acid typically contains about 85% Typical specifications for the commercial product are as follows:

Another suitable polymeric fatty acid material is a mixture of polymerized fatty acids predominating in trilinoleic acid. A particularly satisfactory acid is commercially available from the W. C. Hardesty Company under the trade name of D-50 Acid. Another suitable product is marketed byRohm & Haas Company under the trade name VR-l Acids. Such'acidsmay be:

U.S. 2,470,849 issued to w. E. Hanson May 24, 1949. The

mixture of high molecular weight unsaturated fatty acids comprises monomers, dimers, trimers and higher polymers in the ratio of from about 45% to about 55% of a monomers and dimers fraction having a molecular weight in the range of from about 300 to 600, and from about 45% to about 55% of a trimers and higher polymer fraction having a molecular weight in excess of 600. The fatty acid polymers result in part from a thermal polymerization of fatty acid type constituents of the castor oil, and in part from other reactions, such as the intermolecular esterification, of such acid to form high molecular weight products. The acid mixture, which is mainly a mixture of polymeric long chain polybasic carboxylic acids, is further characterized by the following specifications:

Acid No.-l50 to 164 Saponification No.l75 to 186 Freefatty'acids-575 to 82% Iodine value44 to 45 As noted in the above US. patents, the lubricating oil solvent extract can be used as such or air blown, preferablythe latter. A particularly suitable extract is the SAE 20 Chlorex extract oxidized for about 2 /2 hours at about 375 F. and having a Saybolt Universal viscosity at 210 F. of about 95-115 seconds, and an A.P.I. gravity of about 9-12. 5

The blending hydrocarbon oil is preferably a petroleum oil having a Saybolt Universal viscosity, at 100 F. of from about 50 to about 200 seconds, although more viscous oils can be used. The blending oil can be a light lubricating oil, preferably a wax distillate, although other petroleumoil fractions within the desired viscosity range can be used, for example, cracking still cycle stocks.

Although the coal spray composition of the present invention can be formulated without an asphalt, it is preferred that from about 10% to about 20% of an asphalt be incorporated. The asphalt can be one having a softening point of from about 70 F. to about 125 F., and preferably from about 80 F. to about 90 F.

Depending upon the type of coal to be treated and climatic conditions encountered, the finished coal spray composition should preferably have a Saybolt Universal viscosity at 100 F. of from about 500 to about 3000 seconds, and a flash point above about 300 F.

The following examples are illustrative of coal spray compositions of the present invention: 7

Example Composition 7 Solvent extract, percent; 45. 75 46. O 53. 75 60. O0 Solvent extract, perceut 59. 4 Blending oil, percent 40 50 38.00 28.00 19. 75 19.8 Asphalt, percent 13. 50 15.50 18. 0O 19. 75 19. 8 Polymerized fatty acid;

percent 0. 25 0. O 0. 25 0. 50 1 Viscosity composition: SayboltUniversal at 100 F.,

seconds 580 790 1, 700 2, 700 3, 000

-Air-blown Chlorex extrarit-SSUiit 210 F.107 seconds.

2 Air-blown phenol extract of an SAE' 10 oil. 3 Mineral oil distillate of 105 S511 at 100 F. 4 8090 F. softening point. 5 Mixture of polymerized fatty acids predominating in tiilinoleic acids. Illinois soft coal sprayed with the above formulations at the rate of 1.75 gallons per ton gave greatly improved coverage over coal sprayed at the same rate with similar formulas, but containing no polymeric fatty acids. Also coal treated with formulations of the present invention weathered very well. I

Unless otherwise specified, percentages given herein and in the appended claims are volume percentages.

I'claim: 1. A coal spraying composition consisting essentially of from about 0.25% to about 5% of a polymeric linoleic acid having a molecular weight of above 300 containing from about 30 to about 60 carbon atoms in a molecule and at least two carboxyl groups, from about 20% to about 50% of a diluent hydrocarbon oil, and from about 40% to about 60% of an extract obtained by the solvent extraction of a lubricating oil, said extract containing essentially cyclic compounds of the group consisting of aromatic compounds, polynuclearnaphthenic compounds, and mixtures thereof.

2. A coal spraying composition as described in claim 1 in which the polymeric linoleic acid is a dimerized linoleic acid. v

3. A coal spraying composition as described in claim 1 in which the polymeric linoleic acid is a polymerized fatty acid composed essentially of about dilinoleic acid, about 12% of trilinoleic acid, and about 3% of the monomeric acid.

4. A coal spraying composition as described in claim 1 in which the polymeric linoleic acid is a mixture composed essentially of from about 45 to about 55% of a linoleic acid monomer and dimer fraction having a molecular weight in the range of from about 300 to about 600 and from about 45% to about 55% of a linoleic trimer and higher polymer fraction having a molecular weight in excess of about 600.

5. A coal spraying composition as described in claim 1 in which the extract is a Chlorex extract.

6. A coal spraying'composition as described in claim 1 in which the extract is a phenol extract.

7. A coal spray composition as described in claim I in which the extract is an air-blown Chlorex extract.

8. A coal spraying composition as defined in claim 1 containing up to about 30% of an asphalt having a softening point of from 70 F. to about 125 F.

9. A coal spray oil composition consisting essentially of' from about 0.25% to about 5% of a mixture of polymeric high molecular weight unsaturated carboxylic acids, said mixture consisting from about 45% to about 55% of a linoleic acid monomer and adimer fraction having a molecular weight in the range of from about 300 to about 600 and from about 45% to about 55% of a linoleic trimer and higher polymer fraction having a molecular weight in excess of 600, from about 20% to about" 50% of a'hydrocarbon oil having a Saybolt Universal viscosity at F. of from about 50 seconds to about- References Cited in the tile of this patent UNITED STATES PATENTS Gray Aug. 28, 1945 Pickell June 26, 1956 OTHER REFERENCES Moore: Paint, Oil and Chemical Review, 13, 14, 16, 26, 28 and 29, January 4, 1951.

UNITED STATES PATENT OFFICE CERTIFICATE OF CGRRECTION Patent No 2,913,349 November 17, 1959 John 1)., Neesley It is hereby certified that error appearsv in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected be'low.

Column 1, line 32, for solven" read solvent line 46, for extracts as" read extracts are column 3, line 6, for "44 to 45" read 44 to 55 column 4, line Al, after "linole'ic" insert acid Signed and sealed this 17th day of May 1960 (SE AL) Attest:

KARL H. AXLINE 7 ROBERT C. WATSON Attesting; Officer Comissioner of Patents 

1. A COAL SPRAYING COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 0.25% TO ABOUT 5% OF A POLYMERIC LINOLEIC ACID HAVING A MOLEUCLAR WEIGHT OF ABOVE 300 CONTAINING FROM ABOUT 30 TO ABOUT 60 CARBON ATOMS IN A MOLECULE AND AT LEAST TWO CARBOXYL GROUPS, FROM ABOUT 20* TO ABOUT 50% OF A DILUENT HYDROCARBON OIL, AND FROM ABOUT 40% TO ABOUT 60% OF AN EXTRACT OBTAINED BY THE SOLVENT EXTRACTION OF A LUBRICATING OIL, SAID EXTRACT CONTAINING ESSENTIALLY CYCLIC COMPOUNDS OF THE GROUP CONSISTING OF AROMATIC COMPOUNDS, POLYNUCLEAR NAPHTHENIC COMPOUNDS, AND MIXTURES THEREOF. 